Manufacture of alkyl aryl sulfonates



Dec. 11, 195e J. W. PUTT VMANUFACTUREZ OF ALKYL ARYL SULFONATES FiledApril 24. 1952 ATTORNEY United States Patent l MANUFACTURE F ALKYL ARYLSULFONATES James W. Putt, Los Angeles, Calif.

Application April 24, 1952, Serial No. 284,041

21 claims. (cl. 26o-sos) This disclosure is concerned vwith a .veryeconomical method for the manufacture vof surface active agents andsynthetic detergents, particularly with the active .ingre dient of suchsynthetic detergents. Generally speaking, there are three classes ofsurfaceactive agents: anionic, .cationic and nonionic. Furthermore,there are various types of organic .chemical compounds included in eachclass. For instance, the anionics may include salts of (l) alkylsulfates, .(2) long chain fatty acids and (3) sulfonic acids ofmononuclear .and polynuclear aromatic hydrocarbons, their alkylatedderivatives and other derivatives of such hydrocarbons. The presentinvention is especially concerned with the sulfonic acid of alkylatedaromatic hydrocarbons, vand salts of such acid. A salient object .ofthis invention is to devise a process whereby such salts can be preparedin a high degree of purity in a very economical manner.

Fhe greatest proportion of the alkyl aryl sulfonate In -the new methodthe olefin employed may be the same as the dodecene used in most of thealkyl aryl types of active sold heretofore. However, -the process is notlimited lto dodecene. For instance, tripolylene (nonylene) diisobutyleneand trsobutylene have 'been employed Vto yield la `very successfulproduct.

' While benzene may be used Aas the aromatic hydrocarbon, it is by nomeans essential.V In `the newmethod it Vis displaced 'by Ia mixture ofaromatic hydrocarbons particularly :those boiling between 390 -FL and600 F. or preferably between 400 F. and l550 F. Essentially this mixtureconsists 'of -alkylfnaphthalens with or Awithout naphthalene itself.While lit -is preferable that this mixture -be substantally free fromnon-aromatic hydrocarbons, it is not essential because Vthey areysubsequently eliminated in the process. The required hydrocarbons,

Y constituting the starting material, :may be obtained from type ofsurface active agent sold at .present consists ofV the sulfonate ofdodecyl benzene. Its manufacture involves the following general steps:

l. 'Preparation of dodecene. 2. Alkylation of benzene by reaction withat least an equivalentquantity of dodecene to form dodecylbenzenefollowed by its separation and purication.

3. Sulfonation of the .dodecylbenzene with a large excess of fumingsulfuric acid. l

4. Neutralization of the sulfonationl mixture to yield the active,sodium dodecyl `benzene sulfonate, ,admixed with a large proportion ofsodium sulfate.

5. Extraction of the sulfate-sulfonate mixture with ethyl alcohol toseparate the sulfonate and separation of the alcohol therefrom.

6. Drying.

Builders such as polyphosphate, borax, carbonate may be added before orsubsequent to step .6. To a large extent step 5 is .a Apresent omittedVbecause .it is very expensive, and because the product :otherwise wouldYbe hygroscopic. The omission, of course, leaves a product withaverylarge proportion of sodium sulfate, an undesirable 'feature because itlimits the concentration of surface active agent Iin the nisheddetergent and causes 'a disagreeable reaction of the detergent .on thehands Y of petroleum naphtha required.

ln the new method of the invention for the production of alkyl arylsulfonates, both the starting substance land the steps of the processare modified in a novel manner so that the product is obtained at avastly reduced cost.

coal tar or the like. -l-n sharp lcontrast with fbenzene, the chemicalydemand for =the v390 F.-600 F. is not great. -lt Ais easily -procurableata -steady'price -Fu'rthermore, yespecially of 'great importance thisfraction forms a large proportion `of the product from'the subjection ofcertain petroleum fractions of wide boiling range in accordance with myVPatent lNo.2,207,-552, and may be derived from such product 'by simplefractionation.

As hereinabove stated, the prevalent Vmethod used for the production ofalkyl aryl sulfonates -involves the interaction of benzene and ,at'least an -equimolecular quantity of olefin, followed by Athe isolationand vpurification of alkylated vbenzene andthe sultonation of thisproduct with :turning sulfuric acid ina distinctly separate step.

in striking contrast, -in the -new method, sulfonation takes place inthesame kettle in which the alkylation step is carried out Without yany-priorseparation 'whatsoever. Aromatic hydrocarbon, olen and sulfuricVacid are .all mixed in a kettle to yield the desired sulfonic acid ofthe .alkylated aromatic hydrocarbon in one Vsimple process step. Whiledue .to the possibility y.that alkylation proceeds at a faster .ratethan .does sulfonation, alkylation may actually take placesrst',followed by sulfonation, to all intents Aand purposes from va practicalstandpoint, alkylationand sulfonationare .carried .out in one step withagreat saving in plant Ainstallation vcost and opertaing cost. Y

The new Ymethod has a .further important economic advantage in that ithas been found that because .of peculiar properties .of ythe .mixture.of aromatic hydrocarbons, .an equimolecular :quantity of oleiin'is notrequired. quantity of oleiin gave a good product. This .is .quite aneconomicgadvantagein yiew .of the .fact that lthe olen is more costlythan .the-aromatic hydrocarbon mixture especially .when the latter isprepared in .accordance with Patent No. 2,207,552. Furthermore,ginthe..presence of so low a Vrelative quantitycf volefin .there is veryVlittle Vor no likelihood 4:for .polyalkylation and esteriiication ofthe sulfonic acid -to take place.

The aromatic mixture -used inthe .process is much more .easilysulfonatedthan is benzene. As a Yresult the.

sulfonation can be carried out .With98% sulfuricV acid although turningacid 4can/be used. acid would not be suitable. However, ithas ,beenfound that the required reaction can be carried out with greaterfacility by using stronger acid than 9,8%, preferably ,by starting outwith '98% sulfuric Vacid to the extent of about 30%60% of the total acidrequired and thenv completing the reaction with Istronger acid such as5% to 20% fuming 4sulfuric acid.

lt has been stated above that :the sulfonationofdodecyl benzene requiresalarge excess of sulfuric acid. This is also true in the vcase of thelmixture of varomatic hydrocarbons `used in ,the :present process.However, in :the

In fact, Vas little as 30% of an -equimolecular With benzene 98% 'Y"fuging the sulfonic acid layer. Vthe ability to recover this excessacid results in three very modity.

A embodiment of the process.

case of 'dodecyl benzene, the dried sodiumsalt of the sulfomc acid isquite hygroscopic and is therefore sold in admixture with a highconcentration of sodium sulfate in order to overcome this difficulty.`To provide this sodium sulfate, the excess sulfuric-acid is neutralizedtogether with the sulfonic acid. YA product containing sodium sulfonateVadmxed with a large proportion of sodium sulfate results. Thisoperation'fnecessarilv requires a large expenditure of sodiumhydroxide;VY This is dlsadvantageous because itdepreciates a largequantity of 'sulfuric acid, a fact of quite some yconcern in these daysof short supply of sulfur. .It consumes large quantities of sodiumhydroxide Yand Yresultsinra product with a lowv concentrationofacrtive.'V Furthermore, wheneven despite the hygroscopicity, a productwith `ahigh concentration of surface active agent is desired, theexpensive step of alco-` hol. extraction has to be resorted to becauseof the large quantity of sulfuric acid sulfonic acid. Y Y

`With the/aromaticrmixture usedl in thisV process, however, theresulting Vsodium sulfonate is non-hygroscopic and can thus bemaintained exposed toVordinary-'atmo'sthat remains dissolved in thephere Without danger lof* caking or of vany other defect.

Because of the highv concentration in which the surface active agent canbe prepared, the range of finished detergents has f beenV enhancedtremendously. Furthermore.l

this high concentration of surface active agent canibe procured quitesimplyfbecause the greater part of the excess sulfuric acid separates bygravity from the Sulfonic acid and is therefore easily recoveredtherefrom. A further quantity of sulfurieacid is obtained upon centri-As will be appreciated.

important economic advantages: The recovered sulfuric :acid is madeavailable for further use, a factor of extreme importance becauseY ofthe very short supply of this corn- Secondly, ja great-savingv inthecost of alkali is V"achieved because alkaliV does'nothave to be usedto'neu- Vtralize this excess acid. Finally, the surface active agent isrecovered in very high concentrations because it is notfaccoinpanied byvery large quantities-ofY sodium sulfate asin the prior processen, I, Y1 l Any residualy sulfuric acid remaining ,adr-mixed .withthe sulfonicjacid is removed *by conversion by addition Vof lime to calciumlsulfateandjseparated by filtration.V Thu's Vtheprocess -is capableY ofproducingsurface 'activerv agent accompanied Yby'little or no sodium'sulfa'tealthough a small proportion yfisallowed to remain because 1t acts asY`abulder.l f 'H In orderto insure' a clear understandingof the newprocess and an evaluation 'of itsfnjeritsgreference is made to theaccompanying drawing which illustrates but one vAsrshownin the drawing,a Ypetroleum oil,V prefer-ahh.'

Vone the major portion of which/boils between 400 and V600"VFisltaken'rfrom storage 1 and is continuously passed 'Y to Van`extraction unit 2. "Any" solvent such as sulfur dioxide, furfural or'thelike which will eliciently separate the parajns from the otherhydrocarbons, particularly the aromatics and ole'tinrs, may be employed.Treatment in the extraction unit leads to the formation of a raflinatewhich Vishwithdrawn throughline 3 and an extract withdrawnthroughlin'e4; The solvent is removed: from both the rainate and V.extract by'suit-able. means, not shown.V The Yraliinate is removed. from Ythesystem as one of the 'Y ndproducts fof the process. f Y t The extract isthen subjectedY to cracking at elevated rate through compressor 7 andheater Sbeore it comes in contact with the heated stream of extract inline 6.

The air reacts with some of the heatedroilresulting in Y an increase intemperature to the desired level of about Y 1050 F. to 1200o F.,preferablyfbetween 1125u F. and

1175 F. As is well understood, the quantity of air in aromatizationoccurs, ldepending upon the gravity ;and

sidual ,oil is further processed to lyield pitch with a desired n ilAboiling range of the'raw chargeand reaction temperature.` 20

series of Vseparators 10, 11 and 12. VFromseparat'or `1t) Y The productfrom vreactor 9'is conductedthrough a heavy residual oil is removedthrough line;` 13.V Thisy re.

melt point. The vapors Vfrom separator 10are fractionated in Vessel 11from which is discharged an overhead containingV light products andwater` formed from the Y action 'of the air and extract. The lightproducts `contain combustion products, hydrogen, methane, other paraftnsand olens with V2 to 5 carbon atoms andaromaticslwith 6 t0 9 carbonatoms. This overhead is passed through condenser 14 and accumulator 15wherein waterY is al- Y lowed to separate and is dischargedtherefromthrough lineV 16. Some light oil is returned by means of pump 17 as reuxto fractionator 11rr The remainderis discharged through line 18 tostorage. This oil may be refined by treatment with sulfuric acidras iswell understood and a pre-benzeneY cut removed by fractionation.VV 1

The'remainder containing toluene; yxylenesr, a mixture of C9V aromatichydrocarbons together with' a small quantity of benzene may well beemployed as aviationrich mX- *V i l i ture or separated into individualVcomponents., Alterdischarged .from tower 12 Vthrough. line'v 20.toVstorage.`

This oil may beV later treated toseparate carbazole-free i anthracenesuitable for oxidation. to anthraquinonei j ',The detergent stock leavesYas vaporlhfromthe upper portion of tower 112,1is passed through cooler21, ,thenceVV nately the light oil may iirst beA fractionated,particularly` to separatealphamethyl styrene,.before being subjected Vtochemical treatment. Y 1

g vThe 'uncondensed portion of the products may be separated inaccumulator 15, discharged through line19and" Y Y conducted to anabsorption system toreover condensible Y y products therefromand'maythen be employed as fueljor ared. Y

The portion is passed to fractionator 12.Y Herein detergent Vstockboilingbetween 390"V and 550 Ffis separated as ,an Aoverhead. from aheavier and higher .boiling oil which has the A' characteristics ofYanthracene oil. .The anthracene oilis to accumulator 22. Arportion isreturned as redux by temperaturesparticularly in ,theV presence of anextraneousVY gas; In`the particular embodiment chosen, airYV is Vused asthe extraneousgas whichserves to provide autogenous yheat. 'The extractis pumped to arheater 5 .where'it is heated to about 700 F. and thenceconducted to line 6 where it meetsand is mixedwith aV stream of heatedair. airhad'previouslybeen passed Tat Va predetermined Ythetype hereindescribed; j Y

means of pump 23 toto'werlZ and 'the remainder con verted to detergent.VDependent upon', factors extraneous to the'. matter or `detergents,'itmaybe'gdesirable to separateA Y Y a part or all .ofthe naphthalene`fromV the detergent stock. This can be .done inany knownmannenisuch asbyclose fractionation. The naphthalenecanthen be marketed as such orconverted to derivatives such as phthalic anhydride, beta-naphthol,naphth'ylramineor to adeterg'entpfV Before thek detergent stock Y haslto be chemically treated. g VThe art of treatingdeter- Vgenttstocl isthe'same as that'practiced in the prepara tion of pure aromatic'hydrocarbons such as benrzenerrand Y toluene,AV destinedV forthemanufacturero dyesand:medieV Y of the product tower llvaboiling.generially above 390 F., leaves the tower at Ythe bottom and Y is. converted,however, it 'f 5 cinals. Therefore, the treating process will notY bedescribed in detail. However, it should be noted that the detergentstock should first be treated with alkali to remove phenolic compounds,then with acid recovered in a later step, to extract nitrogen bases. Thephenolic compounds and nitrogen bases can be recovered by neutralizingtheir respective solutions. It is economically advantageous to do this.v

After the oilhas been freed from acidic and basic constituents, it istreated one or more times with a relatively small amount of sulfuricacid. Spent acid obtained in a later step can advantageously be employedfor at least a part of the reiining treatment followed by commercial 66B. sulfuric acid in an amount equal to a total of from to 20 lbs. perbarrel, in two steps. With proper care known in thetreating of aromatichydrocarbons and lubricating oil, the acid-treated oil is washed andthen redistilled. It is then ready for conversion to active ordetergent.

The description of the new process followed to convert the detergentstock into surface active agent and detergent may be more easilyunderstood by study of the following' mol. equivalent of nonylene isemployed. Thus both naphthalene and nonyl naphthalene derivativesarepresentv in the final product. The reactions may bel represented asfollows:

(i) CH3 where R is the radical remaining upon removal of H from Thecompound designated by RSOsNa is, of course, the desired surfaceactive'agent. s l

In' carrying out the process, the. treated detergent stock is.transferredto a jacketed kettlel 24 equippedwith. agritator; the valves26 and 27 remain closed during the-whole sulfonation reaction. An olefinsuch as tripropylene, tetrapropylene or other olein or mixture ofolenscontaining 8 to 18 carbon atoms is also charged to the kettle 24. YThe quantity of oleiin may vary between 10 and 100- mol percentdepending upon the boiling range of the-.aromatic'hydr'ocargon mixture,the olen employedand the l quality of the surface active agent desired.A surface Vactive'agerrtofv high quality has been obtained from theV useof: 310 mol percent of tripropylene. The olefin and aromaticvhydrocarbon are thoroughly, mixed. by means ofthe stirren The-mixtureis then subjected to an alkyl- Y ation-and sulfonation reaction in onestep. Sulfuric acid-A is used'zin both reactions: tained .in operation,sulfuric acid of 98% concentration- While the stirreris ,mainor.vstronger is at first added? slowly at such rate that the temperaturedoes not rise above about 105 F. to 110 F. A. streamv of cold water ispassed through the jacket of the kettleA to control this temperature.Usually it takes 20'to 30 minutes to add the acid in a volume equal toVabout 1/2 of the total volume of detergent stock and olefin. When such avolume of acid has been added, another like volume of acid is added tothe reaction mixture. This can be done more quickly and without the aidof the cold stream of water. A period of about 10 minutes can be takenfor such addition. Thus the total volume of acid employed is equal tothe total volume of hydrocarbon undergoing reaction. Stirring ispreferably continued but the reaction is aided by allowing a stream ofhot water to pass through the jacket to raise the temperature of thereaction mass to about 145 F. and to maintain it at this point until thesulfonation is complete.

AsV the reaction proceeds, the mass which is reddish in color, becomesmore and more viscous.` The end of the reaction is determined by notingthe behavior of a drop of reaction mass on a glass wall. A shinyappearance alkali or sodium carbonate.

` completion a large volume of dense stable suds is obhas reached about15% of the total original hydrocarbon volume. ably decreases.

The Viscosity of the mass then notice- The volume of' added water isnoti critical. More than the noted volume may be employedr Without harmto the reaction. However, such increasedk volume increases the cost ofdrying the finished product. A periodV ofabout' l0 minutes is generallyrequired for the addition of the water. Stirring is then stopped and'Athe mass allowed to remain in a quiescent state; This permits excesssulfuric acid or'a part thereof, to separatel asa lower'layer from thesulfonic acid. Water, equal inA volume to about V5% of the originaltotal volume of, hydrocarbons, is then very slowly and carefully poureddown one' side of kettle 24. Upon intermingling with the' acid mass, thewater causes the separation of a layer of oilthat had not beensulfonated, either due to actual incompleteness of the reaction orbecause some unsulfonatable oil was originally present, or both.

With this procedure a three-layer system is obtained, the sulfonic acidbeingV established between an upper layer of' o'il, lgenerally about 10%of the volumeY of the original detergent stock, and a lower layer ofsulfuric acid.4 About 20 minutes is allowedV for separation to takeplace. The vlower layer'of sulfuric acid isthen withdrawn through lines33 and 28 by opening valve 27 and is passed through line 2S to storagefor later concentration or conversion to useful products such asammonium sulfate or copper sulfate. After complete removal of thesulfuric acid, valve 27 is closed and valver'26 is opened and thesulfonic acid is then separated from the unsulfonated oil andtransferred to jacketed kettle 29v through lines 323 and 3S' for furtherpurification. After such separation kettle 24 is vavailable for anothersulfonation batch.' lf desired, the' sulfonic acid may iirst Y besubjected toa centrifugal action in centrifuge '30,

- whereby a further amount of free sulfuricV acid is separated andwithdrawn'through line 28. Lines 33,734

and 35YA are. unusually large in diameter on account of Some freesulfuric acid amounting to about20 to 30% Y,

- detergent builders.

Y as hot air or hot combustion gases.

known in the art and therefore need not be describedi 60" Ytom eithercontinuously through line 41 by VmeansY of a 'the detergent dried'indrier 40.V l

of that originally added still remains 'dissolved inthe sulfonic acid.This is neutralized by means of Vlime added in kettle 29 which islequipped with'stirrer. The contents'of this kettle are agitated andYcooled by meansV of a stream of cold water passing'throughf the jacket5 31V;V From hopper 32, lime slightly in excess of the amountVequivalent to the free vsulfuric acid in the sulfonic acid mass isadded and caused to react with the acid mixture. Sufhcient time isallowed to insure 'substantially complete reaction with the sulfuricacid. At l least Asome, of the excess lime neutralizes an equivalentamount of sulfonic acid. VThe calcium sulfonate formed, however, remainsdissolved in the sulfonic acid to by far'the largest extent. Y

'Afterfcompletion of Vthe neutralization,reaction, the 15 contents ofthe kettle are discharged from the bottom andare passed to thefilter.The calcium sulfate formed in kettle 29, together with any lime'that mayhave escaped A reaction, is thus separated from the'sulfo'nic acid byfiltra? tion. The ltrate is then passed'toneutralization tank 20 38. Thefilter 36 may be of any. known type and may,

if desired, even be replaced by a centrifuge. f

Therdesired surface-active compound is the sodium salt of the sulfonicacid. The sulfonic acid is converted to its-sodiumvsalt byneutralizationwith an equivalent amount of sodium hydroxide solution.-The'quantity of alkali is-very critical becauserthe addition of too`much would leave free alkali associatedv with the finishedr detergent,an undesirable situation as Vis now very well known. On the otherhand,the use of an insufcient 30 amount would, of course, leave free sulfonicacid. This similarly is undesirable because it would interfere with thedrying` of the finished detergent, would lgreatly decrease its qualityasY a washing compound'and would Y produce a corrosive product. However,the addition of an Vinsufcient quantity of alkali` can be corrected -ata later step. A very good method Yto follow Vis to add alkali until themass becomes-neutral as indicated Vby'a pH of 7. 'i

The nsolution at this point may contain a small amount 40' of calciumVsulfonate as a result of theprior addition of more lime than wasnecessary'to neutralize the free sulfuric acid in the sulfonic acid.This calcium sulfonate is converted to the4 desired corresponding sodiumsalt by Y adding thereto sodium carbonate or its aqueous solution notdecreasein anyV way the quality ofthe detergent because/sodium carbonateis recognizedas one of 'the' v The last step in the process involves theVremoval ofy the water from the solutionof the Vsurface Aactivecomipound. This is accomplished by transferring the filtratel fromfilter 39 to drier 4! wherein the water is evaporated by means ofindirect yheat, exchange with hot gases such This step is well TheYdried surface active agent is withdrawn at theV botscrew orintermittently. Water vapor and other gases orf vaporsle'ave the drierat the top through line 42.

Surface-active Vcompounds .infa'"concentrat1on of 90% or overfareYobtained inthis manner. Builders such as Y phosphates, polyphosphates,borax, carbonates ,orV siliagents such Vas lauryl sulfate f andrvmodierssuch` asy y carboxy methyl cellulose may also be added. However, any orall oftheseY substances mayalso be addedrtoA the.

Vsolution of surface active agentvr in tank13`8,`jwherein they canVbecome intimately mixed, Vandthe solutioniiof 7 t times itehas beenkfound that hydrcxizarbon.r oil'inay remain dissolved in the solution ofsurface active agent.

This oil reduces the quality of the finished detergent; i ItV matichydrocarbon mixture as described above, it appears that alkylation isvirtually completerbeforethe sulfonation reaction sets in to any degree.case, some olefin would be in contact with sulfonic acid and Ysulphuricacid. Bothof these acids are esterication catalysts. and thereforesomeesterication would befex-V pected. lf esters wereV formed, they would be present in the oil obtained upon the careful addition of waiterV tothe sulfonic acid.V This oil was analyzedandwwas Vfound to containVlessV than 1% of sulfonic ester. YIn view of the fact that the volumeof the oil constituted only about 10% ofk the volume of originalaromatic hydrocarbons, ester formation took place to the extent of lessVthan 0.1%, a negligible quantity.

The process as described involved the subjection of th -V Yraw feed .toanV extractionv step followed by a` thermal cracking reaction, toprepare the aromatic" hydrocarbon Vmixture for thealkylation-sulfonation step in kettle 24.

These steps may be modified in several ways without in l any wayaffecting the nature'nor the novelty of the pr`oc`V ess. Forinstancefthe raw feed may be made to undergo one of several catalyticcracking processes, such as Fluid,

TCC, Houdry, followed by separation of gasoline, lighter'V Y productsand fuelV oil, and subjection of thecrackedY product boiling betweengasoline andfuel oil to the cracking step in reactor 9. Furthermore,insteadjof. interact-v ing oil vapors'with air, they may be subjected todirect vheat Yexchange relationship with hot combustion gasesor anyother gas heated in sucient'quantity and to a sufliciently high degreeVso asto heat the oil vapors in reactor 9 to a temperature of 10570"F..to 1200" F. y

The cracking step of the processas effected in reactor'. 9 has beendescribed as being purely thermal. YHowever, y

natural or synthetic catalysts ofthe types used in ordinary petroleumcatalytic cracking process -may `Vbe employed effectively. Y

, Furthermorea portion'of coal tar boiling'between V 390 F. and 600 F.'before or Vafter removal of naphthalene may be chemicallyl treated*Ywith alkaliV and sulfurie acid as described above in connectionuwith thepurifcation Vof the detergentV cut frornaccumulator'ZZ, and thensubjected to the Valkylation-'sulfonationYj.reaction,Y withoutundergoing Yanyextraction or'cracking steps whatsoever, to yield anacceptable detergent..

In an'example of one'embodiment of theprocess,"ex tract from diesel oilboiling between 407 F; and 600 F.V

was vcharged under a pressure of 60 p. sgi. g. toY heater f 5 at therate of 9.3V G. P. H., and heatedV to a temperature ofj700fa Atljunction Y6 theroil vapors werebrou'ght in intimatecontact withn astream ofV air flowing through heater 8 at the rate Vot 320 C. F. /hr.VAfter mixing, .the

temperature rose V-to 1170 Ff CrudeV aromatics were Y formedinafvolumetricY yield of 77.67% which, upondistillation, gave 38.01%detergent'cut, based on charge to heater 5,- 4.85 aviation richvmixture, 2.18%'fresinlcut (350 F. to 400'F.);and 32.56%v anthracene oil,pitch and distillation loss'. Y The .detergent cut was treated con--4secutively with 35% NaOH to remove tarV acids, recovl ered ;H2SO4toremove tar bases, twice with'J 66 Be. VVH2804 in aV quantity'of 8.6lbs/bbl. to improvecolor and-j then redistilled. A-portion. of thetreated detergentcut, f '230 cc., wasmixed Vwith 70 cc'.offt'riprop'ylene' inaaski equipped with a stirr'er. TotheY mixture in acooll waterV bath was addeddu'r'inglminutes 150 cc. of 98%H2SO4.

aty such rate that the,temperatureldidA not rise above 1107"- F.iThewater-bath was thenremoved and camere If this were not the amasseof 98%,H2504 was added during 5.. minutes. Tri.: mixture was then heated on afhotV water bath; whereby the temperature was allowed toy rise to, 145 F.wl'iile-tllfev stirring Vof the mixture, now quite. viscous, wascontinued. In about l minutes, tests as above; explained, showed thatthe alkylationrsulfonation reaction was practically complete. 50 cc. ofwater was added slowly and the mixture transferred to aseparatoryfunnel.` Sulfuric acid began to separateimmediately. About 20,cc. water was allowed to run down the wall whereby unsulfonated oilbegan to rise from the sulfonic acid. The excess acid layer was removedfollowed by thesulfonic acid leaving 22 cc. unsulfonatedoil. Io, thesulfonic acid was added 50 gms. of lime, thoroughly mixed and the CaSOiseparatedVv by lti-ation. The filtrate was neutralized by addingY 30%NaOH until' the pH was raised to 7. The solution was then-heated and toitwas added a small quantity of NaCOa solution unt-il-t-hepllof thesolution was raised to 8. Calcium carbonate" precipitated. This wasseparated byjiltratiorr;V ltrate was washed twice, with benzene and thenheated to drive o t the water.

A lght'colored slurry was `obtained which analysis` showed to containactive in a concentration wel over 90% on a Water-free basis and in ayield of over 80% of the theoretical, based on the detergent stockcharged.

The product formed a large amount of long lasting dense suds and upon awashing test after addition of sodium tripolyphosphate and carboxymethyl cellulose, was found to have a very high degree of detergency andwhiteness retention.

lt is to be noted that in processes known heretofore, a surface activeagent with a high degreeot" detergency can be obtained only byextraction of the active solution with a solvent such as alcohol. Thisis expensive. in the described process, a product with a higherconcentration of surface active agent than any anion surface activeagent generally on the market is-obtained without the necessity or" analcohol extraction of the sulfonate solution.

The process has been especially described in connection with the sodiumsalt of the sulfonic acid. Similar sulfonate of other metals or ofammonium, alkyl ammonium, or hydroxy-ammonium compounds can be preparedin the same manner by employing the oxide or hydroxide of the desiredmetal or ammonium derivatives as the neutralizing agent. The sulfonatesof the alkaline earth metals such as calcium deserve attention, fortheir preparation is quite easy since all that is needed is to add anexcess of metal oxide to the mixture of sulfuric acid and sulfonic acid.The calcium sulfonate solution is easily separated by filtration fromthe precipitated calcium sulfate and the water evaporated by known meansfrom the solution to obtain the dry sulfonate. This saves many stepsthat are necessary in the preparation of the corresponding sodiumsulfonate.

The method of'producing anionic detergentsV herein described has beendirected toward the fraction essentially aromatic hydrocarbons boilingbetween 390 F. and 600 F. as the feed to the detergent reaction. it hasbeen found, however, that equally eiective detergents can be prepared byutilizing the lower boiling aromatic oil boiling between 180 F. and 390F., and even the broader cut boiling between about 180 r. and 600 F. Y

as the feed. ln utilizing this fraction containing the lower boilingaromatic hydrocarbons, it was found desirable` but not absolutelynecessary to separate the fraction boiling between about 360 F. and 390F. from which proplyene benzene can be isolated. The use of 98% sulfuricacid followed by stronger acid, as has already been described above, isofl especial bene't when detergentsV are made from oil containing thecut boiling between 180 F. and 300 F. to 400 F. Y

While preferred modifications of the inventionr have been described, itis to be understood that these are given didacticaily to illustrate theunderlying principles in- 1:0 volved and not as limiting its usefulscope to the particular'illustratedj embodiments.

Iclaim:

l. A'process of producing anionic surface-active com-` pounds whichcomprises simultaneously alkylating and sulfonating a mixture ofaromaticy hydrocarbons having a boiling range within the limits fromsubstantially 390 F. to substantially 600 F., with an olefin inthepresence of sulfuric acid in a'single'reaction zone; agitating thereaction mixture in said smgle reaction zone until alkylation andYsulfonation are substantially completely eected, adding water tothereacted mixture in amounts-and under conditions'controlled to effectlayer separation of free ysulfuric acid, unsulfonated oil and alkylaryl` sulfonic acid, separating thelayers, recovering the alkyl arylsulfonic acid and neutralizing the sulfonic acid with basic material4 toform the corresponding alkyl aryl sulfonates.

2.A-process in accorda-nce with claim 1 in which the quantity-of olefinen iployexi' isfless thang-an equimolar quantity of the aromatichydrocarbons.

A3.Y A process in4 accordanceV with claimy l; in; whichj the sulfuricacid employed-in. thereaction comprises; substan- 4. A process inaccordance with claim l in which the..

aromatic hydrocarbon mixture has a boiling range of from substantiallywithin 430 F.5 00 F.

- 5. A process in accordance with claim 1 in which the aromatichydrocarbon mixture is comprised preponderantly of alkyl naphthalenes.

6. A process in accordance wtih claim 1 in which the aromatichydrocarbon mixture is comprised preponderantly of alkyl naphtha'leneand is substantially free from basic and acidic constituents.

7. A process in accordance with claim l in which the aromatichydrocarbon mixture is derived from cracked petroleum oil.

8. VA process in accordance with claim l in which the aromatichydrocarbon mixture is derived from coal tar distillates.

9. A-process in accordance with claim 1 in which the separated alkylaryl sulfonic. acid is treated with an alkaline earth reagent in amountssu'icient to react with and oil.

ll. A process in accordance with claim 1 in which the olen is chosenfrom the group consisting of dodecene, tripropylene, diisobutylene andtriisobutylene. Y

12. A process in accordance with claim l in which the aromatichydrocarbon mixture has a boiling range of from substantially 180 F. to600 F.

13. A process in accordance with claim l in which the olen is added tothe extent of 30 to 70 mol percent in relationship to the hydrocarbon. y

14. A method of producing an alkyl aryl sulfonate from petroleum oilwhich comprises ysubjecting a petroleum fraction boiling within about250 F. and 600 F. to the solvent action of SO2 to extract thenon-parainic hydrocarbons, separating the solvent from such non-paranichydrocarbons, subjecting such hydrocarbons to cracking conditions oftemperature and pressure controlled to prol ing between about 390 F. and600 F. treating the separated fraction to remove therefrom the phenoliccornpounds and nitrogen bases; simultaneously alkylating and sulfonatingthe purified separated fraction with an olen in the presence of strongsulfuric acidy in a singleireaction zoneV while agitating thev reactionmixturel for a period of time suliicient to substantially complete Vthe@gasses alkylation and sulfonation reactions; adding vvater to' the treaction product in an amount and under conditions concipitate -analkaline earth sulfate, VYneutralizing the thusV treated sulfonicV acidwith a basic material, separating the liquid from V'the precipitate,treating the neutralized product'with an alkaline carbonate to yieldsubstantially a pH of 8, andseparating the precipitate byliltrationrVfrom the Valkyl'aryl sulfonate. f

-16.,A^ process in accordance with claim 14 in which the f sulfuric acidemployed inthev "reaction comprises 98% sulfuric acid. f f 1 17.7Aprocess in accordance with claim 1,5 in which prior to drying thealkyl-aryl sulfonate is extracted Vwith a selective solvent to removeany contained unsulfonated oil.

;1'21 u 18. vprocess in accordance with' claim 14 in which therelationship'to the aromaticv hydrocarbon.

' 19. A process in accordance with claim 14V in which the sulfonic acidis converted to an alkali metal salt. t

' 20. Aprocess in accordance with claimV 14 in which. the sulfonic acidis converted to Van alkaline earth salt. Y V21. A process in accordancewith claim 14 in vwhich the quantity of olefin employed is less Vthan anequimolar 'Y 1'0 quantity of the aromatic hydrocarbon.V

'References Citedrin thefle of this patent Y f STATES PATENTS Y 152,072,153 Brusoneta1., 1 25 1 fMar.72, 1937 2,227,999 v Y Brandt etal. 1Jan.V 7, 1941 2,652,427 Y Shultz sr sept.,15,-1953 2,655,530 V`Nevisoli,Oct. v13, 1953 20 f Y Y OTHER REFERENCES Y 4Schwartz-Perry: SurfaceActive IAg'entS, Interscience r Pub1ishers,1949,pp.116,124.. Y

olefin is added tothe extent of 30% to 70- mol percent `in

1. A PROCESS OF PRODUCING ANIONIC SURFACE-ACTIVE COMPOUNDS WHICHCOMPRISES SIMULTANEOUSLY ALKYLATING AND SULFONATING A MIXTURE OFAROMATIC HYDROCARBONS HAVING A BOILING RANGE WITHIN THE LIMITS FROMSUBSTANTIALLY 390* F. TO SUBSTANTIALLY 600* F., WITH AN OLEFIN IN THEPRESENCE OF SULFURIC ACID IN A SINGLE REACTION ZONE; AGITATING THEREACTION MIXTURE IN SAID SINGLE REACTION ZONE UNTIL ALKYLATION ANDSULFONATION ARE SUBSTANTIALLY COMPLETELY EFFECTED, ADDING WATER TO THEREACTED MIXTURE IN AMOUNTS AND UNDER CONDITIONS CONTROLLED TO EFFECTLAYER SEPARATION OF FREE SULFURIC ACID, UNSULFONATED OIL AND ALKYL ARYLSULFONIC ACID, SEPARATING THE LAYERS, RECOVERING THE ALKYL ARYL SULFONICACID AND NEUTRALIZING THE SULFONIC ACID WITH BASIC MATERIAL TO FORM THECORRESPONDING ALKYL ARYL SULFONATES.